▎ 摘　　要

The bifunctional oxygen catalysts are crucial to the commercialization of metal-air batteries. In this work, two-dimensional polymerized cobalt phthalocyanine (PPcCo) is combined with three-dimensional graphene (3D-G) through 7C-7C interaction to obtain the PPcCo/3D-G bifunctional oxygen catalysts. The delocalized 7C-bonds of PPcCo provide greater electron delocalization energy. The 7C-7C interaction between the PPcCo and 3D-G not only solidly anchors PPcCo and fully exposes the Co-N4 sites but also enhances the performance of the catalyst. The PPcCo/3D-G exhibits excellent electron conduction, a large specific surface area, and a rich pore structure for enhanced mass transfer. In terms of electrochemical performance, the oxygen reduction reaction (ORR) halfwave potential (E1/2) of PPcCo/3D-G catalytic is 0.860 V vs RHE and the electron transfer number of PPcCo/3D-G is 3.95 (@0.740 V vs RHE). The small overvoltage (AE = Ej = 10 -E1/2) of PPcCo/3D-G is 0.780 V. Furthermore, the Zinc-air battery (ZAB) with PPcCo/3D-G as the cathode catalyst has high power density (347 mW cm-2), specific capacity (776 mAh g-1), smaller charge/discharge polarization, and significant long-term stability. The flexible all-solid-state ZAB (FZAB) with PPcCo/3D-G as the cathode catalyst also exhibits excellent performance. These results suggest that the PPcCo/3D-G is available as an efficient cathode bifunctional catalyst for ZAB and FZAB.